Stable conditioning shampoo containing anionic surfactant/cationic conditioning agent - non-volatile silicone emulsion

ABSTRACT

A hair conditioning shampoo composition comprising an emulsion of water; about 5 to about 65 percent by weight of an anionic cleaning surfactant, such as ammonium lauryl sulfate; from about 0.1 to about 20 percent by weight of a cationic di-long chain alkyl quaternary nitrogen-containing conditioning agent, wherein the long alkyl chains bonded to the nitrogen atom have from about 12 to about 22 carbon atoms per alkyl chain, such as distearyl dimethyl ammonium chloride; from about 0.5 to about 10 weight percent of a long chain fatty alcohol having about 8 to about 32 carbons in the long chain, such as stearyl alcohol; from about 0.5 to about 10 weight percent of a non-volatile silicone; and about 0.1 to about 5% of an anionic cross-linked polymeric suspending agent, such as a polymer of 2-acrylamide-2-methylpropane sulfonic acid.

FIELD OF INVENTION

This is a continuation in part of application Ser. No. 07/552,437, filedJul. 13, 1990 now U.S. Pat. No. 5,034,218.

The present invention is directed to a hair conditioning shampoocomposition and to a method of treating hair with the composition tocleanse the hair and, at the same time, to provide the hair withunexpectedly improved wet stage and dry stage conditioning properties aswell as other conditioning properties, such as softness, withoutresidual build-up of conditioning agents on the hair. More particularly,the present invention is directed to a hair conditioning shampoocomposition including one or more anionic cleaning surfactants, such asammonium lauryl sulfate, one or more non-volatile silicone oils, such asa polydimethylsiloxane compound, a water-insoluble, oil-soluble di-longchain alkyl, quaternary ammonium salt conditioning agent, a long chainfatty alcohol, and an anionic polymeric suspending agent, such as apolyacrylic acid suspending agent. Surprisingly, and contrary to theteachings of the prior art, the anionic surfactant/cationic di-longchain alkyl quaternary ammonium salts are compatible, when combined withan anionic polymeric suspending agent, to effectively suspend thenon-volatile silicone oils in the composition without the problem ofanionic surfactant-cationic conditioning agent incompatibility.

BACKGROUND OF THE INVENTION AND PRIOR ART

Soiled human hair is shampooed to remove sebum, that is naturallysecreted by the head, as well as soil and other atmospheric contaminantsthat accumulate on the hair. Sebum, in particular, accumulates on thehair in a relatively short period of time leaving the hair with agreasy, dirty feel and poor manageability. The most effective shampoosfor cleansing the hair for removal of the atmospheric contaminants andsebum, are those that contain high lather synthetic anionic detergents,such as the long chain alkyl sulfates and the partially ethoxylated longchain alkyl sulfates. These synthetic anionic detergents are veryeffective for cleansing the hair but, after rinsing with water, leavethe hair with a dried touch, usually called "creak" and result in hair,when wet, that is in an extremely tangled and unmanageable after-shampoocondition.

Thoroughly cleansed hair is extremely difficult to comb, in either thewet or dry state because the individual hair fibers tend to snarl, kink,and interlock with each other. Particularly prior to complete drying ofthoroughly cleansed hair, in this after-shampoo stage, the hair is verydifficult to comb or brush. Even after complete drying, the thoroughlycleansed hair remains difficult to comb or brush and does not set well.Thoroughly clean, dried hair also has undesirable electrostaticproperties in a low humidity atmosphere that causes the hair to "flyaway", thereby further reducing the combing or brushing property of thehair. Generally, these above-outlined problems that result fromsynthetic detergent cleansing of the hair, particularly the high-lathersynthetic anionic detergents, have been elevated either by theafter-shampoo treatment of the hair with hair conditioners, for examplein the form of a hair rinse, or by including hair conditioners directlywithin the shampoo composition.

After-shampoo hair conditioning compositions are easily formulated butare inconvenient to use because of the necessity of applying theconditioner to the hair in a separate stage, after shampooing. Thepreparation of a conditioning shampoo has been more difficult because ofinherent incompatibility problems between anionic surfactants and thefatty cationic compounds that are good conditioning agents. Contactbetween an anionic surfactant and a cationic surfactant or cationicpolymer produces a precipitate that forms immediately or causes aninteraction between the anionic and cationic compounds thatsignificantly reduces their respective cleaning and conditioningproperties. The reduction in cleansing and conditioning effectiveness isobserved even in compositions wherein the anionic and cationic compoundsdo not precipitate from the composition but remain in solution orsuspension. This incompatibility between an anionic surfactant and acationic conditioning compound is well recognized by those skilled inthe art. For example, Sagarin in Cosmetics, Interscience Publishers,Inc., New York, p. 538 (1957), states that anionic and cationiccompounds cannot be used in combination because they react to forminsoluble salts.

A partial solution to this incompatibility problem in the formulation ofconditioning shampoos is exemplified by the following patents thatdisclose compositions that contain surfactants that are not anionic e.g.non-ionics, amphoterics and zwitterionics together with cationicconditioning compounds: U.S. Pat. No. 3,849,348 to Hewitt; U.S. Pat. No.3,990,991 to Gerstein; and U.S. Pat. No. 3,822,312 to Sato.

Another problem inherent in formulating a conditioning shampoo is aninstability problem that results when water-insoluble conditioningagents are also included in the conditioning shampoo composition, suchas the non-volatile silicones that are well recognized in the art asproviding a degree of softness to the hair.

Silicones in shampoo compositions have been disclosed in a number ofdifferent patents: U.S. Pat. No. 2,826,551, Mar. 11, 1958 to Green; U.S.Pat. No. 3,964,500, Jun. 22, 1976 to Drakoff; U.S. Pat. No. 4,364,837,Dec. 21, 1982 to Pader; British Pat. No. 849,433, Sep. 28, 1960 toWoolston; U.S. Pat. No. 4,741,855 to Grote, et al.; U.S. Pat. Nos.4,788,006 and 4,902,499 to Bolich, Jr. et al. and U.S. Pat. No.4,704,272 to Oh et al.

A particularly difficult problem to solve in silicone-containingconditioning shampoos is that of keeping a dispersed, insoluble,non-volatile silicone material suspended in stable form while retainingthe cleansing and conditioning performance of the conditioning shampoo.The stability problem is particularly prevalent in conditioning shampooslike those disclosed herein containing an anionic surfactant and acationic conditioning material which, as outlined above, by themselvestend to interact and present stability problems. A variety of materialshave been proposed for inclusion in silicone-containing conditioningshampoos for purposes of thickening and stabilization such as xanthangum, long chain acyl derivatives, long chain amide oxides, and longchain alkanolamides as disclosed in U.S. Pat. Nos. 4,788,006; 4,704,272;and 4,741,855.

SUMMARY OF THE INVENTION

In accordance with the principles of the present invention, it has beenfound, surprisingly, that a conditioning shampoo containing an anionicsurfactant, a cationic di-long chain alkyl quaternary ammonium salt, along chain fatty alcohol, and a non-volatile silicone material hasextended product stability, excellent cleansing properties and providesunexpected overall conditioning to human hair, particularly superior wetand dry combing properties when combined with an anionic cross-linkedpolymeric suspending agent.

Surprisingly and unexpectedly, compositions of the present invention arestable and do not exhibit the inherent anionic surfactant/cationicconditioning agent incompatibility. It was further surprisingly andunexpectedly found that hair treated with the composition of the presentinvention is thoroughly cleansed and exhibits improved physical andcosmetic properties, such as gloss, thickness, manageability, softnessand body. Further, it was surprisingly and unexpectedly found that hairtreated with the compositions of the present invention does notexperience build-up on the hair shaft, over time, of conditioningagents, as is common with many conditioning shampoo compositions.

Therefore, an aspect of the present invention is to provide ahair-treating composition that cleanses the hair and imparts improvedphysical properties and cosmetic properties to the hair in a singleapplication.

Another aspect of the present invention is to provide a physicallystable conditioning shampoo containing an anionic surfactant, a cationicconditioning agent, and a non-volatile silicone.

Another aspect of the present invention is to provide a new and improvedconditioning shampoo containing a strong anionic detergent, such as along chain alkyl sulfate, long chain alkyl ether sulfate, and/or longchain sulfonate, that is compatible with a cationic quaternary ammoniumconditioning agent and a non-volatile silicone conditioning agent, thatis unexpectedly stable due to an anionic polymeric suspending agent.

Still another aspect of the present invention is to provide a new andimproved conditioning shampoo including about 5% to about 65% of ananionic surfactant; about 0.1% to about 20% of a cationic,nitrogen-containing conditioning agent having only two long chain alkylradicals bonded to the nitrogen atom, the long chain radicals havingpredominantly about 12 to about 22 carbon atoms per long chain alkylradical; about 0.5% to about 10% of a non-volatile silicone material;about 0.5% to about 10% of a long chain fatty alcohol and about 0.1% toabout 5% of an anionic, polymeric suspending agent.

A further aspect of the present invention is to provide a new andimproved method of making an aqueous conditioning shampoo having ananionic surfactant, a cationic nitrogen-containing conditioning agent, asuspended non-volatile silicone, a fatty alcohol, and an anionicpolymeric suspending agent by solubilizing the silicone or silicones inthe quaternary nitrogen containing conditioning agent, and vigorouslymixing the composition, together with the polymeric suspending agent, afatty alcohol, and a portion of the anionic surfactant to suspendsilicone droplets having a particle size in the range of about 5 micronsto about 100 microns to provide new and unexpected stability to theconditioning shampoo composition, without sacrifice in foaming.

The above and other aspects and advantages of the present invention willbecome apparent from the following detailed description of the preferredembodiments.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The aqueous conditioning shampoo composition of the present inventiongenerally includes an anionic surfactant in an amount of about 5% toabout 65% by weight of the composition; a cationic di-long chain alkylquaternary ammonium salt in the amount of about 0.1% to about 20% byweight of the composition; a water-insoluble fatty alcohol in the amountof about 0.5% to about 10% by weight of the composition; one or morenon-volatile silicones in an amount of about 0.5% to about 10% by weightof the composition; and an anionic polymeric suspending agent, such as across-linked polyacrylic acid in the free acid form or partially orcompletely neutralized polyacrylic acid, in an amount of about 0.1% toabout 5% by weight of the composition.

The conditioning shampoo of the present invention provides the hair withimproved physical and cosmetic conditioning properties, such as gloss,thickness, softness, and manageability, including excellent wet and drycombing properties and body. As will be demonstrated more fullyhereinafter, it is surprising and unexpected that the composition of thepresent invention, including an anionic cleansing compound, a cationicconditioning compound and a non-volatile silicone material remainsstable, while achieving excellent cleansing and conditioning.

The anionic cleansing surfactant used in the composition and method ofthe present invention can be any of the anionic surfactants known orpreviously used in the art of hair shampoos. An anionic cleansingsurfactant should be included in the composition of the presentinvention to effectively cleanse the hair and generates a high, stablefoam level that consumers equate with cleaning efficiency. Nonionic andamphoteric surfactants are not as effective in cleansing the hair and donot provide the high foam level desired by consumers. However,optionally, nonionic, amphoteric and/or zwitterionic surfactants can beincluded in the compositions of the present invention in addition to oneor more anionic surfactants, to help stabilize foam, to provide asuitable viscosity, or to give other functional or esthetic propertiesto the composition.

Usually, the anionic cleansing surfactant includes a hydrophobic moiety,such as a carbon chain including from about eight carbon atoms to about30 carbon atoms, and particularly from about twelve carbon atoms toabout twenty carbon atoms and further includes a hydrophilic moiety,such as a sulfate, sulfonate, carbonate, phosphate or carboxylate.Often, the hydrophobic carbon chain is etherified, such as with ethyleneoxide or propylene oxide, to impart a particular physical property, suchas increased water-solubility or reduced surface tension, to the anioniccleansing surfactant.

Suitable anionic cleansing surfactants include, but are not limited to,compounds in the classes known as alkyl sulfates, alkyl ether sulfates,alkyl ether sulfonates, sulfate esters of an alkylphenoxypolyoxyethylene ethanol, alpha-olefin sulfonates, beta alkyloxy alkenesulfonates, alkyl arylsulfonates, alkyl carbonates, alkyl ethercarboxylates, fatty acids, succinamates, sulfosuccinates, sarcosinates,octoxynol or nonoxynol phosphates, taurates, fatty taurides, sulfatedmonoglycerides, fatty acid amino polyoxyethylene sulfates andisothienates; or combinations thereof. Many additional anionic cleansingsurfactants are described in McCUTCHEON'S DETERGENTS and EMULSIFIERS,1989 ANNUAL published by McCutcheon's Division MC Publishing Company,herein incorporated by reference. Usually, the anionic cleansingsurfactant is present in the composition as a neutralized salt in theform of a sodium, potassium, lithium, ammonium, alkylammonium orhydroxyalkylammonium salt, wherein the alkyl moiety includes from one toabout three carbon atoms. The alkyl sulfates and alkyl ether sulfatesare particularly effective classes of anionic cleansing surfactants.Exemplary anionic cleansing surfactants that are useful in thecomposition and method of the present invention include, but are notlimited to, the ammonium, monoethanolamine, diethanolamine,triethanolamine, isopropylamine, sodium, potassium, lithium, ormagnesium salts of lauryl sulfate, dodecylbenzenesulfonate, laurylsulfosuccinate, lauryl ether sulfate, lauryl ether carboxylate, laurylsarcosinate, cocomethyl tauride, and sulfosuccinate half ester amide; orcombinations thereof. An especially useful anionic cleansing surfactantis a mixture of a lauryl sulfate salt and a lauryl ester sulfate salt.

The emulsified conditioning shampoo of the present invention alsoincludes a cationic water-insoluble, emulsifiable conditioning agent.The cationic conditioning agent used in the emulsified conditioningcomposition and method of the present invention is an oil-soluble,water-dispersible di-long chain alkyl quaternary ammonium salt,particularly a di-long chain alkyl, di-short chain alkyl quaternaryammonium salt. Oil soluble, water-dispersible quaternary ammoniumcompounds useful in the composition and method of the present inventionare quaternary ammonium compounds having two long chain alkyl groupsincluding from about 12 to about 22 carbon atoms. The long chains can bepredominantly 12, 14, 16, 18, 20 and/or 22 carbon atoms in length andcan be only one chain length or can be mixed chain lengths. Theremaining two substitutions present on the quaternary nitrogen of thequaternary ammonium compound can be hydrogen; benzyl; short chain alkylgroups, having 1 to 4 carbon atoms such as methyl, ethyl, orhydroxyethyl; or combinations thereof, as long as the quaternaryammonium compound is oil-soluble and water-dispersible and contains twolong chain alkyl substitutions, as defined.

The anion of the oil-soluble quaternary ammonium compound can be anyanion, such as chloride, bromide, methyl sulfate, acetate, phosphate ornitrate, as long as the quaternary ammonium compound is oil-soluble.

In accordance with an important feature of the present invention, theoil-soluble, water-dispersible conditioning agent included incompositions of the present invention are those having a quaternarynitrogen atom and two long alkyl chains, having from about 12 to about22 carbon atoms per alkyl chain. These conditioning agents include awide range of compounds that can be broadly divided into groups basedupon the structure of the substitution on the quaternary nitrogen atom,i.e., (a) compounds having two long carbon chains and one or twoidentical or different short chain alkyl groups having one to four,particularly one or two carbon atoms, and (b) compounds having two longcarbon chains, one benzyl group and one short chain alkyl group havingone to four, particularly one or two carbon atoms. The following list ofoil-soluble quaternary ammonium compounds are exemplary, but notlimiting, of oil-soluble di-long chain alkyl quaternary ammoniumcompounds that can be used in the composition and method of the presentinvention:

    ______________________________________                                        Distearyldimethyl-                                                                             (Distearyl dimonium chloride);                               ammonium chloride                                                             Distearyldimethyl-                                                                             (Distearyl dimonium bromide)                                 ammonium bromide                                                              Dicetyldimethyl- (Dicetyl dimonium bromide);                                  ammonium bromide                                                              Dimethyldi-      (Quaternium-18);                                             (hydrogenated tallow)-                                                        ammonium chloride                                                             Dicetylmethylbenzyl-                                                          ammonium chloride;                                                            Dicetyldimethyl- (Dicetyl dimonium chloride)                                  ammonium chloride                                                             Dicocodimethyl-  (Dicoco dimonium chloride)                                   ammonium chloride                                                             Dicocodimethyl-  (Dicoco dimonium bromide)                                    ammonium bromide                                                              Dibehenyl/diarachidyl-                                                                         (Dibehenyl/diarachidyl                                       dimethyl ammonium                                                                              dimonium chloride)                                           chloride                                                                      Dibehenyl/diarachidyl-                                                                         (Dibehenyl/diarachidyl                                       dimethyl ammonium                                                                              dimonium bromide)                                            bromide                                                                       Dibehenyl dimonium                                                                             (Dibehenyl dimonium methyl                                   methyl sulfate   sulfate)                                                     Hydroxypropyl bis-                                                                             (Hydroxypropyl bis-stearyl                                   stearyl-ammonium dimonium chloride)                                           chloride                                                                      Dibehenyldimethyl-                                                                             (Dibehenyl dimonium chloride)                                ammonium chloride;                                                            Dibehenylmethyl-                                                              benzyl-ammonium                                                               chloride;                                                                     Dimyristyldimethyl-                                                                            (Dimyristyl dimonium bromide)                                ammonium bromide;                                                             Dimyristyldimethyl-                                                                            (Dimyristyl dimonium chloride)                               ammonium chloride                                                             ______________________________________                                    

Wherein the name in parenthesis is the compound name given in the CTFADictionary.

It should be noted that the long alkyl chains of the oil-solublequaternary ammonium compound are not commonly of a single chain length,but a mixture of chain lengths primarily within the C₁₂ -C₂₂ range, e.g.C₁₂, C₁₄, C₁₆, C₁₈, C₂₀ and/or C₂₂. Generally, the oil-solublequaternary ammonium compounds used in the compositions of the presentinvention have the long alkyl chains as a mixture of alkyl lengths. Suchdi-long chain alkyl quaternary ammonium compounds function in accordancewith the principles of the present invention as long as the quaternaryammonium compound is oil-soluble and water-dispersible. Suchconditioning agents are prepared conveniently from naturally occurringmaterials, such as tallow, coconut oil, soya oil and the like, or fromsynthetically produced mixtures which are known to include a mixture oflong chain radicals.

The water-insoluble emulsifiable conditioning agent useful in thepresent invention should have the ability to separate from water andform a two-phase composition in water when the conditioning agent ismixed with water, prior to emulsification of the composition of thepresent invention. To achieve the full advantage of the presentinvention, the water-insoluble, emulsifiable quaternary ammoniumconditioning agents used in the compositions of the present inventionhave a water-solubility of less than one percent. Such agents may beemployed either as liquids or as solids.

Fatty alcohols useful in the present formulations are primary orsecondary alcohols having about 8 to about 32 carbons, inclusive, eitheras single long chain lengths (e.g. 8, 10, 12, 14, 16, 18, 20, 22, 24,26, 28 or 30 carbon atoms in length) or as a mixture of long chainlengths in any combination. The fatty alcohols can be straight chain,branched, saturated, and/or unsaturated structures and can be used aloneor in admixture with each other. The preferred fatty alcohols arestraight-chained, primary alcohols having about 10 to about 26 carbons,or mixtures of 10, 12, 14, 16, 18, 20, 22, 24 and/or 26 carbonsincluding without limitation, lauryl, tridecyl, myristyl, cetyl,stearyl, oleyl, behenyl, arachyl, carnubyl, and ceryl alcohols, andcombinations thereof. In addition, mixtures of natural or syntheticfatty alcohols having fatty chain lengths of from about 8 to about 32carbons, inclusive, also are useful. Several such mixtures arecommercially available, and are exemplified by a material containing amixture of synthetic alcohols with 12 to 15 carbons in the alkyl chainsold under the trademark NEODOL 25 by Shell Chemical Company, and amaterial containing a mixture of synthetic alcohols with chain lengthsof 12 to 16 carbons sold under the trademark ALFOL 1216 Alcohol byConoco Chemicals.

Other suitable alcohols include the fatty alcohols of the abovedescribed carbon chain lengths which are ethoxylated to contain one toabout three, and, preferably, and average of one or two moles ofethylene oxide per mole of fatty alcohol can be used in place of thefatty alcohols themselves. Examples of such useful fatty alcoholsinclude ethylene glycol cetyl ether, polyoxyethylene (2) stearyl ether,and the like; the exemplary compounds having CTFA Dictionary names ofCeteth-1 and Steareth-2, respectively.

The composition of the present invention also includes from about 0.15%to about 10%, and preferably from about 1.0% to about 5.0%, by weight ofa non-volatile silicone compound. The preferred non-volatile siliconecompound is a polydimethylsiloxane compound, such as a mixture, in abouta 3:1 ratio, of a low molecular weight polydimethysiloxane fluid and ahigher molecular weight polydimethylsiloxane gum. The non-volatilepolydimethylsiloxane compound is added to the composition of the presentinvention in an amount sufficient to provide improved combing andimproved feel (softness) to the hair after shampooing. As referred toherein, "silicone gums" are those nonfunctional siloxanes having aviscosity of from about 5 to about 600,000 centistokes at 25° C. Theso-called rigid silicones, as described in U.S. Pat. No. 4,902,499,herein incorporated by reference, having a viscosity above 600,000centistokes at 20° C, e.g. 700,000 centistokes plus, and a weightaverage molecular weight of at least about 500,000 also are useful inaccordance with the present invention.

Preferred silicone gums include linear and branched polydimethylsiloxanes, of the following general formula:

    (CH.sub.3).sub.3 SiO--[Si(CH.sub.3).sub.2 O].sub.n --Si(CH.sub.3).sub.3,

wherein n is from about 2,000 to about 15,000, preferably from about2,000 to about 7,000. Silicone gums useful in compositions of thepresent invention are available from a variety of commercial sources,including General Electric Company and Dow Corning.

Examples of suitable preferred anionic, cross-linked polymericsuspending agents useful in the compositions and methods of the presentinvention include cross-linked polyacrylic acid and cross-linked metalsalts of poylacrylic acid (partially or fully neutralized); andcross-linked maleic anhydride.

Any cross-linked, anionic polymer can be used as the suspending agent inthe compositions and methods of the present invention. Suspending agentsshould suspend the silicone materials in the aqueous phase of thecomposition so that the composition remains stable at 120° F. for atleast two weeks. Cross-linked anionic polymers useful for thecompositions and methods of the present invention include those thathave one or more substituents such as carboxylate, carboxy acidanhydride, sulfonate, sulfate, and/or phosphate, which in contact withwater ionize to form polymeric ions with a substantial plurality ofnegatively charged sites. Examples of suitable cross-linked anionicpolymers include:

styrene acrylate/ammonium methacrylate copolymers;

styrene/acrylate copolymers;

styrene/maleic anhydride copolymers;

ethylene/maleic anhydride copolymers;

polyacrylic acid;

styrene/acrylate/acrylonitrile copolymers;

styrene/acrylonitrile copolymers;

poly(vinyl sulfate);

poly(methacrylic acid);

poly(sodium 4-styrenesulfonate);

polyacrylonitrile;

poly(2-acrylamido-2-methylpropane sulfonic acid); and

crosslinked terpolymers of ##STR1##

In this terpolymer, the formation of a gel structure with subsequentthickening occurs after hydrolysis (ring-opening) and neutralization.##STR2##

If hydrolyzed in the presence of competing reactive moieties, especiallyalcohols and amines, esterification or amidation, respectively, may alsooccur. Esterification is believed claimed to further stabilize the ge.1network. The hydrolysis at 60° C is complete in 2 hours, and thereaction path is believed to greatly favor hydrolysis of the ring overany esterification side reactions. Once the ring is opened, admixedalcohols or amines will not react with the carboxylate groups.

Suitable organic polymers include, for example, polymeric water-solublepolyelectrolytes preferably having a molecular weight of at least150,000 and containing a substantially linear carbon chain backbonederived by the polymerization of an aliphatic unsaturated group. Thesepolymers are polymeric organic substances which, when contacted with anaqueous medium, will form organic ions having a substantial number ofionizable groups distributed at a plurality of positions thereon.

One type of compound useful in the practice of the invention is theequimolar copolymer of a polycarboxylic acid derivative and at least oneother monomer copolymerizable therewith. The polycarboxylic acidderivative may be maleic anhydride, maleic acid, iumaric acid, itaconicacid, citraconic acid, aconitic acid, the amides of these acids, thealkali metal, alkaline earth metal and ammonium salts of these acids,the partial alkyl esters, salts of the partial alkyl esters and thesubstituted amides of these polycarboxylic acids. The carboxylic acid,carboxylic acid salt, amide and substituted amide radicals are theionizable groups which contribute to the hydrophilic properties and tendto make the polymers anionic. The corresponding derivatives ofmethacrylic crotonic or other polymerizable acids also are useful, forexample, a copolymer of dialkyl maleate and acrylic acid.

When the hydrophilic maleic acid, acrylic acid, and the like derivativesare used, hydrophobic comonomers may be used, for example, ethylene,propylene, isobutylene, styrene, α-methylstyrene, vinyl acetate, vinylchloride, vinyl formate, vinyl alkyl ethers, alkyl acrylates and alkylmethacrylates. In the practice of this invention the dibasic polybasicacid derivatives of the copolymers may be, for example, maleic acid,maleic anhydride, sodium maleate, potassium maleate, ammonium maleate,calcium maleate, monosodium maleate, monopotassium maleate, monoammoniummaleate, monocalcium maleate, and a monoalkyl maleate, maleic acidamide, the partial amide of maleic acid, the N-alkyl substituted maleicacid amide, the N-amino ethyl maleamide, the N-aminoethyl maleimide, thealkylaminoalkyl maleamides, and the corresponding derivatives ofitaconic, catraconic, fumaric and aconitic acids. Any of theabove-identified polybasic acid derivatives may be copolymerized withany of the other monomers described above, and any other monomer whichforms a copolymer with di-basic acid derivatives. The polybasic acidderivatives may be copolymerized with a plurality of comonomers.

Other suitable cross-linked, anionic polymers are the polymers ofacrylic or methacrylic acid derivatives, for example, acrylic acid, thealkali metal and ammonium salts of acrylic acid, methacrylic acid, thealkali metal and ammonium salts of methacrylic acid, acrylamide,methacrylamide, the N-alkyl substituted amides, the N-aminoalkylamides,and the corresponding N-alkylaminoalkyl substituted amides, theaminoalkyl acrylates, the aminoalkyl methacrylamides and the N-alkylsubstituted aminoalkyl esters of either acrylic or methacrylic acids.These polymeric compositions may be the homopolymers or they may becopolymers with other copolymerizing monomers such as ethylene,propylene, isobutylene, styrene, o-methylstyrene, vinyl acetate, vinylformate, alkyl ethers, acrylonitrile, methacrylonitrile, vinyl chloride,vinylidene chloride, the alkyl acrylates, the alkyl methacrylates, thealkyl maleates, and the alkyl fumarates, and other olefinic monomerscopolymerizable therewith.

Another class of cross-linked anionic organic polymers are the polymersof vinyl sulfonic acid, and the copolymers of vinyl sulfonic acid withone or more polymerizable organic monomers, for example, vinyl chloride,acrylonitrile, styrene, vinyl acetate and other polymerizablemono-olefinic compounds. The sulfonic acid groups so introduced may beconverted to sulfonic acid salts, acid amides or other electrolyticgroupings. The copolymers of this type may involve the use of aplurality of sulfonic acid monomers and/or a plurality of theconventional comonomers as described.

The cross-linked anionic polymers should have a weight average molecularweight of at least about 50,000, preferably at least about 150,000, andbest results are achieved when the cross-linked anionic suspending agenthas a weight average molecular weight of at least about 1,000,000.

One particularly effective crosslinked anionic suspending agent is acopolymer of acrylamide or substituted acrylamide, and sulfonic acid orits derivatives. One example is poly(2-acrylamide-2-methylpropanesulfonic acid) sold under the trademark RHEOTHIK 80-11 by HenkelCorporation of Ambler, Pa. for cosmetic applications. RHEOTHIK 80-11 hasa viscosity at 25° C of 200,00 cps, an acid value of 43.0 and a pH of2.0. Other particularly effective crosslinked anionic suspending agentsare the terpolymers of methyl vinyl ether, maleic anhydride and astraight or branched chain diene having double bonds at the first andlast positions, e.g. 1,9-decadiene. One such terpolymer is sold by GAFCorporation under the trademark GANTREZ ACV-4006.

To achieve the best stability, a portion of the water and a portion ofthe anionic surfactant(s) are mixed first and heated to a temperatureabove the melting point of the fatty alcohol, e.g. 150-200° F. The fattyalcohol then is added until it is completely dissolved in the water. Thesilicone or silicone blend then is added and the mixture is agitatedvigorously to shear and break up the silicone material into dropletspreferably to a size less then about 10 micrometers, and more preferablyto a size of about 5 microns to about 100 microns. The mixture ismaintained at a temperature above the melting point of the fatty alcoholuntil all components are added. Prior to adding the di-long chain alkylquaternary ammonium salt, it is preferred to increase the temperature upto about 175° F. to 190° F. After the silicone is dispersed and thetemperature is increased to least about 175° F., preferably about 180°F. to about 185° F., the di-long chain alkyl quaternary ammonium salt isadded, with agitation, to form an emulsion.

Two particularly useful anionic, crosslinked polymers are the copolymersof acrylamide and a sulfonic acid or a substituted sulfonic acid, e.g.,poly(2-acrylamide-2-methylpropane sulfonic acid) RHEOTHIK 80-11 ofHENKEL COMPANY; and terpolymers of a vinyl ether and a straight orbranched chain diene having double bonds at the first and last positionsand a carbon chain length of about C₅ to about C₁₈, e.g., a terpolymerof methyl vinyl ether, maleic anhydride and 1,9-decadiene, e.g., GANTREZACV-4006 slurry of GAF Corporation.

To achieve the best results, at the point that the silicone is sheared,the composition should have a viscosity in the range of about 5,000 toabout 20,000 centipoises so that upon vigorous mixing or shearing, theresulting silicone droplets have a particle size of about 5 microns toabout 100 microns, and preferably about 10 microns to about 30 microns,and are stable in the oil phase. As an example of the vigorous mixing, asix-bladed axial flow turbine impeller rotating at a speed of about 500to 800 r.p.m. provides sufficient shearing of the non-volatile siliconematerial resulting in silicone droplets within the size range of about 5to about 100 microns, and the sheared silicone droplets areexceptionally stable. Depending upon the quantity of anioniccross-linked polymeric suspending agent used, and the amount of watercontained in the polymer, about 0 to about 20% of the water contained inthe final composition can be withheld from the composition, togetherwith a proportionate percentage of the anionic surfactant, if necessaryto provide a sufficiently viscous composition to shear the silicone,e.g. 5,000 to 20,000 centipoises. To achieve the full advantage of thepresent invention at least a portion of the polymeric suspending agentshould be contained in the composition when the silicone or siliconeblend is sheared for best stability. The shearing of the silicone withina viscous composition provides the best silicone particle size andstability to the composition. If the particle size of the siliconedroplets is less than about 5 microns, the silicone surface area is toogreat resulting in reduced foam. If the particle size of the siliconedroplets is greater than about 100 micons, the silicone droplets have atendency to coalesce and separate from the composition.

If some of the water and surfactant are withheld from the compositionuntil after silicone shearing to maintain the composition sufficientlyviscous during silicone dispersion, the remaining water and anionicsurfactant(s) then are added, slowly, e.g. about 1 to about 3,preferably about 1 to 2, pounds per minute for a 250 pound shampoobatch, with gentle agitation.

Without being bound by any particular theory it is theorized that one orboth of the long chain alkyl radicals from the di-long chain alkylquaternary ammonium salt forms a complex with the anionic surfactantsurrounding the silicone droplets, dispersed in the water phase, to aidin stabilizing the silicone suspension. The cross-linked anionicpolymeric suspending agent appears to enter into this ionic complexingto aid in the suspending of the silicone droplets. Whatever themechanism, contrary to the prior art teachings, this complexingresulting in excellent suspension, works for the di-long chain alkylquaternary ammonium salts but not for the mono-long chain alkyl ortri-long chain alkyl quaternary ammonium salts.

The following examples illustrate various conditioning shampoos made inaccordance with the present invention:

    ______________________________________                                                           EXAMPLE    EXAMPLE                                                            1          1A                                              INGREDIENTS:       % WT.      % WT.                                           ______________________________________                                        cross-linked poly(2-acrylamido-                                                                  25.0       25.0                                            2-methylpropane sulfonic acid)                                                RHEOTHIK 80-11 of HENKEL                                                      company                                                                       sodium laureth sulfate                                                                           25.0       25.0                                            (30% active)                                                                  cocamide MEA       2.0        2.0                                             cetyl/stearyl alcohol                                                                            2.0        2.0                                             non-volatile silicone blend                                                                      3.0        3.0                                             25% SE-30 GUM                                                                 75% SF-96-50 oil                                                              distearyl dimethyl ammonium                                                                      1.5        1.5                                             chloride (AROSURF ® TA-100)                                               ammonium lauryl sulfate (30%                                                                     27.50      27.50                                           active)                                                                       sodium laureth sulfate (30%                                                                      2.50       2.50                                            active)                                                                       ammonium xylene sulfonate                                                                        2.00       2.00                                            soft water         6.4236     6.4236                                          isopropyl myristate                                                                              2.00       --                                              lauryl alcohol     --         2.00                                            NaOH (50% active)  0.25       0.25                                            color, fragrance, preservative                                                                   q.s        q.s                                             ______________________________________                                        PROCEDURE:                                                                              1.) Add poly(2-acrylamido-2-methyl-                                           propane sulfonic acid) RHEOTHIK 80-11 of                                      HENKEL Company and, SLS to tank,                                              begin heating to 180-185° F. with moderate                             agitation.                                                                    2.) At 140-150° F., add cocamide MEA, mix                              until melted.                                                                 3.) At 160-165° F. add cetyl/stearyl                                   alcohol, mix until melted.                                                    4.) Add Silicone Blend when fatty alcohol                                     has melted. Increase agitation to shear                                       silicone blend into droplets, at                                              180-185° F. Mix.                                                       5.) At 180-185° F., add AROSURF ®, mix for                         1/2 hour to one hour or until a smooth                                        glossy appearance is seen and composition                                     has a viscosity of at least 5,000 cps.                                        6.) Very slowly add the remaining anionic                                     surfactants, turn off heat and slow down                                      agitation.                                                                    7.) Add isopropyl myristate, mix 10 min-                                      15 min, add NaOH 50%.                                                         8.) Add dye, then remaining ingredients                                       at 110° F.                                                   ______________________________________                                    

    ______________________________________                                        EXAMPLE 2-5 (wt. %)                                                           INGREDIENTS: 2        3        4      5                                       ______________________________________                                        cross-linked 25.0     25.0     25.0   25.0                                    poly(2-acrylamido-                                                            2-methylpropane                                                               sulfonic acid)                                                                RHEOTHIK 80-11 of                                                             HENKEL Company                                                                ammonium lauryl                                                                            20.0     --       20.0   --                                      sulfate (30% active)                                                          sodium laureth                                                                             --       20.0     --     20.0                                    sulfate (30% active)                                                          ammonium xylene                                                                            4.0      --       4.0    --                                      sulfonate                                                                     cocamide DEA 2.0      2.0      2.0    2.0                                     cetyl/stearyl                                                                              2.0      2.0      2.5    2.5                                     alcohol                                                                       non-volatile 3.0      3.0      3.0    3.0                                     silicone blend                                                                25% SE-30 GUM                                                                 75% SF-96-50 oil                                                              dicetyl dimethyl                                                                           2.24     2.24     2.24   2.24                                    ammonium chloride                                                             (ADOGEN ® 432                                                             PG) (67% active)                                                              ammonium lauryl                                                                            35.0     27.5     35.0   32                                      sulfate                                                                       (30% active)                                                                  sodium laureth                                                                             --       7.5      --     7.5                                     sulfate                                                                       (30% active)                                                                  soft water   3.8336   7.8336   3.3336 7                                       isopropyl myristate                                                                        2.0      2.0      2.0    2                                       NaOH (50% active)                                                                          0.25     0.25     0.25   0                                       color, fragrance,                                                                          q.s      q.s      q.s    q.s                                     preservative                                                                  ______________________________________                                    

    ______________________________________                                        EXAMPLE 6-7 (wt. %)                                                           INGREDIENTS:           6        7                                             ______________________________________                                        cross-linked poly(2-acrylamido-                                                                      25.0     25.0                                          2-methylpropane sulfonic acid)                                                RHEOTHIK 80-11 of HENKEL Company                                              ammonium lauryl ether sulfate/                                                                       13.0     --                                            lauramide DEA blend (38.2% active)                                            sodium laureth sulfate (30% active)                                                                  20.0     31.0                                          lauramide DEA          --       2.0                                           cetyl/stearyl alcohol  3.5      3.5                                           non-volatile silicone blend                                                                          3.0      3.0                                           25% SE-30 GUM                                                                 75% SF-96-50 oil                                                              distearyl dimethyl ammonium                                                                          1.0      1.0                                           chloride (AROSURF ® TA-100)                                               sodium laureth sulfate (30% active)                                                                  11.0     --                                            lauramide DEA          2.0      --                                            ammonium lauryl sulfate (30% active)                                                                 --       31.0                                          ammonium xylene sulfonate                                                                            5.0      --                                            soft water             0.4236   0.4236                                        isopropyl myristate    2.0      2.0                                           NaOH (50% active)      0.25     0.25                                          color, fragrance, preservative                                                                       q.s      q.s                                           ______________________________________                                    

    __________________________________________________________________________    EXAMPLES 8-16 (wt. %)                                                         EXAMPLE     8  9  10 11 12 13 14 15 16                                        __________________________________________________________________________    Cross-linked                                                                              25 25 25 25 25 25 25 25 25                                        poly(2-acrylamido-                                                            2-methylpropane                                                               sulfonic acid)                                                                RHEOTHIK 80-11 of                                                             HENKEL Company                                                                ammonium    20 20 20 20 20 20 20 20 20                                        lauryl sulfate                                                                (30% active)                                                                  cocamide DEA                                                                              2.0                                                                              -- -- 2.0                                                                              -- -- 2.0                                                                              -- --                                        cocamide MEA                                                                              -- 2.0                                                                              -- -- 2.0                                                                              -- -- 2.0                                                                              --                                        lauramide DEA                                                                             -- -- 2.0                                                                              -- -- 2.0                                                                              -- -- 2.0                                       cetyl/stearyl                                                                             2.0                                                                              2.0                                                                              2.0                                                                              2.0                                                                              2.0                                                                              2.0                                                                              2.0                                                                              2.0                                                                              2.0                                       alcohol                                                                       non-volatile                                                                              3.0                                                                              3.0                                                                              3.0                                                                              3.0                                                                              3.0                                                                              3.0                                                                              3.0                                                                              3.0                                                                              3.0                                       silicone blend                                                                25% SE-30 GUM                                                                 75% SF-96-50 oil                                                              distearyl   1.0                                                                              1.0                                                                              1.0                                                                              1.0                                                                              1.0                                                                              1.0                                                                              1.0                                                                              1.0                                                                              1.0                                       dimethyl                                                                      ammonium                                                                      chloride                                                                      (AROSURF ® TA-100)                                                        ammonium    35 35 35 35 35 35 35 35 35                                        lauryl sulfate                                                                (30% active)                                                                  isopropyl   2.0                                                                              2.0                                                                              2.0                                                                              2.0                                                                              2.0                                                                              2.0                                                                              2.0                                                                              2.0                                                                              2.0                                       myristate                                                                     soft water  9.15                                                                             9.15                                                                             9.15                                                                             9.15                                                                             9.15                                                                             9.15                                                                             9.15                                                                             9.15                                                                             9.15                                      NaOH        0.25                                                                             0.25                                                                             0.25                                                                             0.25                                                                             0.25                                                                             0.25                                                                             0.25                                                                             0.25                                                                             0.25                                      (50% active)                                                                  color, fragrance,                                                                         q.s.                                                                             q.s.                                                                             q.s.                                                                             q.s.                                                                             q.s.                                                                             q.s.                                                                             q.s.                                                                             q.s.                                                                             q.s.                                      preservative                                                                  __________________________________________________________________________

    ______________________________________                                        EXAMPLES 17-20 (Wt. %)                                                        EXAMPLE:                                                                      INGREDIENTS:    17     18       19   20                                       ______________________________________                                        cross-linked    32.0   32.0     32.0 32.0                                     poly(2-acrylamido-                                                            2-methylpropane                                                               sulfonic acid)                                                                RHEOTHIK 80-11 of                                                             HENKEL Company                                                                ammonium lauryl 13.0   13.0     13.0 13.0                                     ether sulfate/                                                                lauramide DEA blend                                                           (38.2% active)                                                                ammonium lauryl 7.0    7.0      7.0  7.0                                      sulfate                                                                       *30% active)                                                                  cetyl/stearyl   2.0    2.5      3.0  3.5                                      alcohol                                                                       non-volatile    3.0    3.0      3.0  3.0                                      silicone blend                                                                25% SE-30 GUM                                                                 75% SF-96-50 oil                                                              distearyl dimethyl                                                                            1.0    1.0      1.0  1.0                                      ammonium chloride                                                             (AROSURF ® TA-100)                                                        ammonium lauryl 31.0   31.0     31.0 31.0                                     sulfate                                                                       (30% active)                                                                  isopropyl       2.0    2.0      2.0  2.0                                      myristate                                                                     ammonium xylene 1.0    1.0      1.0  1.0                                      sulfonate                                                                     soft water      7.3    6.8      6.3  5.8                                      NaOH (50% active)                                                                             0.2    0.2      0.2  0.2                                      color, fragrance,                                                                             q.s    q.s      q.s  q.s                                      preservative                                                                  ______________________________________                                    

The suspending results achieved in accordance with the present inventionare particularly surprising in view of the Declaration filed (paper No.7) in the file history of the Oh et al. U.S. Pat. No. 4,704,272. ThisDeclaration made it clear that the di-long chain alkyl quaternaryammonium salts could not be effectively incorporated in conditioningshampoos containing one or more non-volatile silicones because of verypoor stability. The following compositions in TABLE I (PRIOR ART)compared in the Oh et al, file history, and the stability results thatfollow, teach those skilled in the art to avoid the use of di-long chainquaternary ammonium salts in a conditioning shampoo containingnon-volatile silicones:

                  TABLE I                                                         ______________________________________                                        (PRIOR ART)                                                                   COMPONENT               WT. %                                                 ______________________________________                                        Ammonium lauryl sulfate 12.00  12.00                                          Ammonium laureth (3) sulfate                                                                          4.00   4.00                                           Ammonium xylene sulfonate                                                                             2.20   2.20                                           Cetearyl alcohol        1.00   1.00                                           Glycol distearate       0.75   0.75                                           Cocamide MEA            1.00   1.00                                           Xanthan gum             0.75   0.75                                           Dimethicone mixture     3.00   3.00                                           Tricetylmethyl ammonium chloride                                                                      0.50   --                                             Ditallow dimethyl ammonium chloride                                                                   --     0.50                                           Color, perfume, minors, water                                                                         q.s. to 100%                                          ______________________________________                                    

"That when these compositions were placed in clear glass bottles andstored for two weeks at 35° F., 50° F. or 80° F., the following resultswere obtained:"

    ______________________________________                                        Present Invention                                                             Temperature (Oh et al.)    Prior Art                                          ______________________________________                                        35° F.                                                                             No visible sep-                                                                              Clear layer at                                                 aration. Com-  top of                                                         position had   composition. The                                               normal appearance.                                                                           composition had                                                               curdled                                                                       appearance                                         50° F.                                                                             No visible sep-                                                                              Clear layer at                                                 aration. Com-  top of                                                         position had   composition. The                                               normal appearance.                                                                           composition had                                                               curdled                                                                       appearance                                         80° F.                                                                             No visible sep-                                                                              Clear layer at                                                 aration. Com-  top of                                                         position had   composition. The                                               normal appearance.                                                                           composition had                                                               curdled                                                                       appearance                                         ______________________________________                                    

Quite to the contrary, applicants have found that in a conditioningshampoo composition containing an anionic polymeric suspending agent, orguar gum, and one or more non-volatile silicones, a di-long chain alkylquaternary ammonium salt is needed, since a tri-long chain alkylquaternary ammonium salt does not produce sufficient stability.

    ______________________________________                                        EXAMPLE 21                                                                    ______________________________________                                        INGREDIENTS:              Wt. %                                               ______________________________________                                        1      Cross-linked poly(2-acrylamido-                                                                      10.0                                                   2-methylpropane sulfonic acid)-                                               19% active RHEOTHIK 80-11 of                                                  HENKEL Company                                                         2      soft Water             16.0                                            3      sodium lauryl sulfate (30% active)                                                                   27.5                                            4      cocamide MEA (monoethanolamide)                                                                      2.0                                             5      lauryl alcohol         2.0                                             6      non-volatile silicone blend                                                                          3.0                                                    25% SE-30 GUM                                                                 75% SF-96-350 oil                                                      7      distearyl dimethyl ammonium chloride                                                                 2.27                                                   (67% active)                                                           8      ammonium lauryl sulfate (30% active)                                                                 27.5                                            9      soft water             0.45                                            10     myristyl propionate    2.0                                             11     NaOH 50%               0.35                                            12     AXS (ammonium xylene sulfonate)                                                                      6.0                                             13     color, fragrance, preservative                                                                       q.s                                             ______________________________________                                        Manufacturing steps:                                                          1.     Add items 1, 2 and 3 mix with moderate agitation and                          begin heating to 185 F.                                                2.     At about 150 F. add item #4, mix until melted, then                           add item #5, mix well until homogenous.                                3.     At about 180 F. add item #6, turn up agitation to                             partially shear silicone.                                              4.     At 180-185 F. add item #7, mix for 1/2-1 hour until a                         smooth homogenous appearance is seen without                                  particles. Avoid any vortex.                                           5.     Add items 8 and 9 very slowly to viscous phase.                               Addition must be slow to avoid particles. Allow no                            vortex. Turn off heat. Begin cooling.                                  6.     Add item #10, mix well until homogenous.                               7.     Add items 11-13, mix well until homogenous.                            ______________________________________                                        RESULTS:                                                                      pH 80° F.   5-6                                                        viscosity 4/20      4,900 cps                                                 TA                 36,000 cps                                                 After 2 weeks at 120° F.:                                              pH                 5.6                                                        rise 4/20           4,100 cps                                                 TA/.5              30,000 cps                                                 SPECS.:                                                                       pH 80° F: 5.5-6.0; viscosity: 3,000-9,000 cps; TA/.5:                  20,000-70,000 cps                                                             ______________________________________                                    

    ______________________________________                                        EXAMPLE 22                                                                    ______________________________________                                        INGREDIENTS:              Wt. %                                               ______________________________________                                        1      crosslinked            27.5                                                   terpolymer of                                                                 methyl vinyl ether +                                                          maleic anhydride +                                                            1,9-decadiene                                                                 (GANTREZ ACV-4006 slurry                                                      of GAF Corporation) 1.5% active                                        2      sodium lauryl sulfate (30% active)                                                                   27.5                                            3      cocamide MEA (monoethanolamide)                                                                      2.0                                             4      lauryl alcohol         2.0                                             5      non-volatile silicone blend                                                                          3.0                                                    33% SE-30 polysiloxane                                                        67% SF96-350                                                           6      distearyl dimethyl ammonium chloride                                                                 1.5                                                    (67% active)                                                           7      ammonium lauryl sulfate (30% active)                                                                 27.5                                            8      soft water             5.0736                                          9      myristyl propionate    2.0                                             10     AXS (ammonium xylene sulfonate)                                                                      2.5                                             11     color, fragrance, preservative                                                                       q.s                                             ______________________________________                                        Manufacturing steps:                                                          1.     Add items 1 and 2 mix with moderate agitation and                             begin heating to 185 F.                                                2      At about 150 F. add item #3, mix until melted, then                           add item #4, mix well.                                                 3.     At about 180 F. add item #5, turn up agitation to                             partially shear silicone.                                              4.     At 180-185 F. add item #6, mix for 1/2-1 hour until a                         smooth homogenous appearance is seen without                                  particles. Avoid any vortex.                                           5.     Add items 7 and 8 very slowly to viscous phase.                               Addition must be slow to avoid particles. Allow no                            vortex. Turn off heat.                                                 6.     Add item #9, mix well.                                                 7.     Add items 10-11, mix well.                                             SPECS.:                                                                       pH 80° F.: 5.5-6.0; viscosity 4/20, 80° F.: 3,000-9,000         cps; TA/.5: 20,000-70,000 cps                                                 ______________________________________                                    

    ______________________________________                                        EXAMPLE 23                                                                    ______________________________________                                        INGREDIENTS:              Wt. %                                               ______________________________________                                        1      crosslinked            26.0                                                   terpolymer of                                                                 methyl vinyl ether +                                                          maleic anhydride +                                                            1,9-decadiene                                                                 (GANTREZ ACV-4006 slurry                                                      of GAF Corporation) 1.5% active                                        2      sodium lauryl sulfate (30% active)                                                                   27.5                                            3      cocamide MEA (monoethanolamide)                                                                      2.0                                             4      lauryl alcohol         2.0                                             5      non-volatile silicone blend                                                                          3.0                                                    33% SE-30 GUM                                                                 67% SF-96-350 oil                                                      6      distearyl dimethyl ammonium chloride                                                                 1.5                                                    (67% active)                                                           7      ammonium lauryl sulfate (30% active)                                                                 27.5                                            8      soft water             4.0736                                          9      myristyl propionate    2.0                                             10     AXS (ammonium xylene sulfonate)                                                                      3.5                                             11     color, fragrance, preservative                                                                       q.s                                             ______________________________________                                        Manufacturing steps:                                                          1.     Add items 1 and 2 mix with moderate agitation and                             begin heating to 185 F.                                                2.     At about 150 F. add item #3, mix until melted, then                           add item #4, mix well.                                                 3.     At about 180 F. add item #5, turn up agitation to                             partially shear silicone.                                              4.     At 180-185 F. add item #6, mix for 1/2-1 hour until a                         smooth homogenous appearance is seen without                                  particles. Avoid any vortex.                                           5.     Add items 7 and 8 very slowly to viscous phase.                               Addition must be slow to avoid particles. Allow no                            vortex. Turn off heat.                                                 6.     Add item #9, mix well.                                                 7.     Add items 10-11, mix well.                                             SPECS.:                                                                       pH 80° F.: 5.5-6.0; viscosity: 3,000-9,000 cps; TA/.5:                 20,000-70,000 cps                                                             ______________________________________                                    

    ______________________________________                                        EXAMPLE 24                                                                    ______________________________________                                              INGREDINETS:           Wt. %                                            ______________________________________                                        1     crosslinked            26.0                                                   terpolymer of                                                                 methyl vinyl ether +                                                          maleic anhydride +                                                            1,9-decadiene                                                                 (GANTREZ ACV-4006 slurry                                                      of GAF Corporation) 1.5% active                                         2     sodium lauryl sulfate (30% active)                                                                   27.5                                             3     cocamide MEA (monoethanolamide)                                                                      2.0                                              4     lauryl alcohol         2.0                                              5     non-volatile silicone blend                                                                          3.0                                                    33% SE-30 GUM                                                                 67% SF-96-350 oil                                                       6     distearyl dimethyl ammonium chloride                                                                 1.5                                                    (67% active)                                                            7     ammonium lauryl sulfate (30% active)                                                                 27.5                                             8     soft water             3.5736                                           9     myristyl propionate    2.0                                              10    AXS (ammonium xylene sulfonate)                                                                      4.0                                              11    color, fragrance, preservative                                                                       q.s                                              ______________________________________                                              Manufacturing steps:                                                    ______________________________________                                        1.    Add items 1 and 2 mix with moderate agitation and                             begin heating to 185 F.                                                 2.    At about 150 F. add item #3, mix until melted, then                           add item #4, mix well.                                                  3.    At about 180 F. add item #5, turn up agitation to                             partially shear silicone.                                               4.    At 180-185 F. add item #6, mix for 1/2-1 hour until a                         smooth homogenous appearance is seen without                                  particles. Avoid any vortex.                                            5.    Add items 7 and 8 very slowly to viscous phase.                               Addition must be slow to avoid particles. Allow no                            vortex. Turn off heat.                                                  6.    Add item #9, mix well.                                                  7.    Add items 10-11, mix well.                                              ______________________________________                                        SPECS.:                                                                       ______________________________________                                        pH 80° F: 5.5-6.0; viscosity: 3,000-9,000 cps; TA/.5:                  20,000-70,000 cps                                                             ______________________________________                                    

    ______________________________________                                        EXAMPLES 25 AND 26                                                            FORMULATION:            25       26                                           ITEM   COMPONENT            WT. %    WT. %                                    ______________________________________                                        1      crosslinked          20.00    20.00                                           terpolymer of                                                                 methyl vinyl ether +                                                          maleic anhydride +                                                            1,9-decadiene                                                                 (GANTREZ ACV-4006 slurry                                                      of GAF Corporation) 1.5% active                                        2      ammonium lauryl sulfate                                                                            25.00    25.00                                           (30% active)                                                           3      cocamide MEA         2.00     2.00                                     4      cetyl & stearyl      2.00     2.00                                            alcohol                                                                5      non-volatile silicone                                                                              3.00     3.00                                            blend                                                                         25% SE-30 GUM                                                                 74% SF-96-50 oil                                                       6      AROSURF ® TA-100 1.50     1.50                                     7      ammonium lauryl sulfate                                                                            30.00    30.00                                           (30% active)                                                           8      ammonium xylene      2.00     2.00                                            sulfonate                                                              9      soft water           11.65    11.65                                    10     isopropyl myristate  2.00     2.00                                     11     NaOH (50%)           0.25     0.25                                     12     color, fragrance,    q.s      q.s                                             preservative                                                           ______________________________________                                    

Various other polymeric suspending agents, glycol and glycerol stearatesand amine oxides were substituted for the crosslinked anionic polymersof the present invention to determine their effectiveness, as shown inthe following examples 27-39, but only the anionic crosslinked polymersand guar gum were effective in providing stability for at least 2 weeksat 120° F.

    ______________________________________                                        EXAMPLES 27-29                                                                ______________________________________                                        FORMULATION:            27      28    29                                      ITEM   COMPONENT        WT. %   WT. % WT. %                                   ______________________________________                                        1      METHOCEL ® slurry                                                                          20.00   --    --                                             (hydroxypropylmethyl-                                                         cellulose) (2.0% active)                                                 1A   NATROSOL ® slurry                                                                          --      20.00 --                                             (Hydroxyethycellulose)                                                        (2.0% active)                                                            1B   GALACTOSOL ® slurry                                                                        --      --    20.00                                          (Guar Gum) (2.0% active)                                               2      ammonium lauryl  25.00   25.00 25.00                                          sulfate (30% active)                                                   3      cocamide MEA     2.00    2.00  2.00                                    4      cetyl & stearyl  2.00    2.00  2.00                                           alcohol                                                                5      non-volatile     3.00    3.00  3.00                                           silicone blend                                                                25% SE-30 GUM                                                                 75% SF-96-50 oil                                                       6      AROSURF ® TA-100                                                                           1.50    1.50  1.50                                    7      ammonium lauryl  30.00   30.00 30.00                                          sulfate (30% active)                                                   8      ammonium xylene  2.00    2.00  2.00                                           sulfonate                                                              9      soft water       11.65   11.65 11.65                                   10     isopropyl myristate                                                                            2.00    2.00  2.00                                    11     NaOH (50%)       0.25    0.25  0.25                                    12     color, fragrance,                                                                              q.s     q.s   q.s                                            preservative                                                           ______________________________________                                         RESULTS (Examples 27-29):                                                    ______________________________________                                        Example 27 was discarded due to overnight                                     separation at room temperature                                                Example 28:                                                                   pH at 80° F.        8.34                                               pH + 20 drops              7.86                                               of citric acid                                                                pH after 30 drops          5.79                                               of citric acid                                                                viscosity at pH 5.79       1,650                                              cps                                                                           TA                         8,000                                              cps                                                                           separatied before two weeks at 120° F.                                 Example 29                                                                    pH at 80° F.        8.24                                               pH + 20 drops              7.86                                               citric acid                                                                   viscosity at pH 5.73       3.400                                              cps                                                                           TA                         28,000                                                                        cps                                                No separation at 120° F. after 2 weeks.                                ______________________________________                                    

    ______________________________________                                        EXAMPLES 30 AND 31                                                            FORMULATION:               30      31                                         ITEM   COMPONENT           WT. %   WT. %                                      ______________________________________                                        1      polyethylene oxide  20.00   --                                                (POLYOX ®)                                                                (2% active)                                                              1A   polymeric quaternary ammonium                                                                     --      20.00                                             salt of hydroxyethylcellulose                                                 reacted with a lauryl dimethyl                                                ammonium substituted epoxide                                                  (QUATRISOFT ®)                                                            (2% active)                                                            2      ammonium lauryl     25.00   25.00                                             sulfate (30% active)                                                   3      cocamide MEA        2.00    2.00                                       4      cetyl & stearyl     2.00    2.00                                              alcohol                                                                5      non-volatile        3.00    3.00                                              silicone blend                                                                25% SE-30 GUM                                                                 75% SF-96-50 oil                                                       6      AROSURF ® TA-100                                                                              1.50    1.50                                       7      ammonium lauryl     30.00   30.00                                             sulfate (30% active)                                                   8      ammonium xylene     2.00    2.00                                              sulfonate                                                              9      soft water          11.65   11.65                                      10     isopropyl myristate 2.00    2.00                                       11     NaOH (50%)          0.25    0.25                                       12     color, fragrance,   q.s     q.s                                               preservative                                                           ______________________________________                                    

MIXING PROCEDURE (Examples 30 and 31):

In an 800 ml beaker, combine items #1 through #3, as composition A,while stirring and heating to 155° F. In a separate 600 ml beaker,composition B, heat #4 to 180° F. and add #5 and #6. After all AROSURF®is dissolved, add #7 and #8 and cool to 155° F. In a separate 1,500 mlbeaker, composition C, combine item #9 through #12 while stirring atroom temperature. Add composition (A) at 155° F. to composition (C) atroom temperature and mix well. Add composition (B) at 155° F. tocombined composition (C) and (A) and cool to 90° F.

    ______________________________________                                        RESULTS (Examples 30 and 31):                                                 ______________________________________                                        Example 30                                                                    pH as 80° F.     5.76                                                  viscosity               1400 cps                                              TA                      16,000 cps                                            separated at 120° F. before 2 weeks                                    Example 31                                                                    Immediate separation occurred when QUATRISOFT ®                           was mixed with ammonium lauryl sulfate.                                       ______________________________________                                    

    ______________________________________                                        EXAMPLE 32                                                                    FORMULATION                                                                   ITEM        COMPONENT        WT. %                                            ______________________________________                                        1           soft water       25.00                                            2           sodium lauryl sulfate                                                                          25.00                                                        (30% active)                                                      3           cocamide MEA     2.00                                                         (VARAMIDE ® C212)                                             4           cetyl & stearyl alcohol                                                                        2.00                                             5           glycol stearate (ethylene                                                                      1.50                                                         glycol monostearate)                                              6           non-volatile silicone blend                                                                    3.00                                                         75% SF 96-50                                                                  25% SE-30 GUM                                                     7           distearyldimonium chloride                                                                     1.50                                                         (AROSURF ®)                                                   8           ammonium lauryl sulfate                                                                        27.50                                                        (30% active)                                                      9           sodium lauryl sulfate                                                                          2.50                                                         (30% active)                                                      10          soft water       7.40                                             11          isopropyl myristate                                                                            2.00                                             12          color, fragrance,                                                                              q.s                                                          preservative                                                      RESULTS:                                                                                Separated at room temperature overnight.                            ______________________________________                                    

    ______________________________________                                        EXAMPLE 33                                                                    FORMULATION                                                                   ITEM        COMPONENT         WT. %                                           ______________________________________                                        1           soft water        25.00                                           2           sodium lauryl sulfate                                                                           25.00                                                       (30% active)                                                      3           cocamide MEA      2.00                                                        (VARAMIDE ® C212)                                             4           cetyl & stearyl   2.00                                                        alcohol                                                           5           glyceryl stearate 1.50                                            6           dimethicone       3.00                                                        75% SF 96-50                                                                  25% SE-30 GUM                                                     7           distearyldimonmium chloride                                                                     1.50                                                        (AROSURF ®)                                                   8           ammonium lauryl sulfate                                                                         27.50                                                       (30% active)                                                      9           sodium lauryl sulfate                                                                           2.50                                                        (30% active)                                                      10          soft water        7.40                                            11          isopropyl myristate                                                                             2.00                                            12          color, fragrance, q.s                                                         preservative                                                      RESULTS:                                                                                Separated at room temperature overnight.                            ______________________________________                                    

    ______________________________________                                        EXAMPLE 34                                                                    FORMULATION                                                                   ITEM     COMPONENT               WT. %                                        ______________________________________                                        1        soft water              25.00                                        2        sodium lauryl sulfate   25.00                                                 (30% active)                                                         3        cocamide MEA/VARAMIDE ® C212                                                                      2.00                                         4        cetyl & stearyl alcohol 2.00                                         5        stearamide MEA stearate 1.50                                         6        dimethicone             3.00                                                  75% SF 96-50 oil                                                              25% SE-30 GUM                                                        7        distearyldimonium chloride                                                                            1.50                                                  (AROSURF ®)                                                      8        ammonium lauryl sulfate 27.50                                                 (30% active)                                                         9        sodium lauryl sulfate   2.50                                                  (30% active)                                                         10       soft water              7.40                                         11       isopropyl myristate     2.00                                         12       color, fragrance,       q.s                                                   preservative                                                         RESULTS:                                                                             Separated at room temperature overnight.                               ______________________________________                                    

Nonionic, crosslinked ethyl acrylate polymers were substituted for thecrosslinked anionic suspending agents and it was found that about tentimes the amount of nonionic polymer was needed to achieve stability fortwo weeks at 120° F., as shown in examples 35 and 36. In examples 35 and36 the AROSURF® was very difficult to blend and the compositions hadvisible white particles, and low viscosities. Further, the substantialincrease in polymer percentage significantly reduced the lather andchanged the lather feel--the lather being much more slippery than thecompositions including an anionic cross-linked polymeric suspendingagent.

    ______________________________________                                        EXAMPLES 35 AND 36                                                            ______________________________________                                        FORMULATION             35      36                                            ITEM  COMPONENT             WT. %   WT. %                                     ______________________________________                                        1     soft water            20.0    20.0                                      2     ethyl acrylate (ALCOGUM ® L-45)                                                                 7.5     10.0                                            (40%)                                                                   3     sodium lauryl sulfate 20.0    20.0                                            (30% active)                                                            4     cocamide MEA          2.0     2.0                                       5     cetyl/stearyl alcohol 2.0     2.0                                       6     non-volatile silicone blend                                                                         3.0     3.0                                             75% SF 96-50 oil                                                              25% SE-30 GUM                                                           7     AROSURF ® TA-110  1.5     1.5                                       8     sodium lauryl sulfate 7.5     7.5                                             (30% active)                                                            9     ammonium lauryl sulfate                                                                             27.5    27.5                                            (30% active)                                                            10    soft water            6.15    3.65                                      11    isopropyl myristate   2.0     2.0                                       12    NaOH 50%              0.25    0.25                                      13    color, fragrance,     q.s     q.s                                             preservative                                                            ______________________________________                                        MIXING PROCEDURE:                                                             ______________________________________                                        1.    Add item #1 soft water, then add item #2 Ethyl                                Acrylate, begin heating to 185° F.                               2.    Add item #3 mix well, then add item #4 at                                     ≈150° F. Mix.                                            3.    At 160-170° F. add item #5, mix till melted, then                      add item #6 at 170-180°  F. mix ≈15 minutes while              shearing the silicone.                                                  4.    At 180-185° F. add AROSURF ® TA-100, increase                      agitation for good surface turn over, batch                                   should appear viseous. Mix.                                             5.    Slowly add items 8-10 over a period of 10                                     minutes be sure there are no solid particles.                           6.    At around 130-140 add item #11, mix well.                               7.    Add NaOH, then remainder of ingredients                                       under 110° F.                                                    ______________________________________                                        RESULTS (Examples 35 and 36):                                                                      35        36                                             ______________________________________                                        pH 80° F.     5.6       5.5                                            viscosity            2300 cps  3100 cps                                       TA                   4,000 cps 8,000 cps                                      ______________________________________                                    

OBSERVATIONS:

The AROSURF® was very difficult to adequately blend into the"oil-phase". Batchs were mixed with more than enough time at 185° F. butboth contained white particles--Example #35 being the worst. Theviscosity of the batches was very low (below specs.)

    ______________________________________                                        120° F. (2 wks)                                                                        35           36                                               ______________________________________                                        pH at 80° F.          5.1 (drifted)                                    viscosity                    3600 cps                                         TA 80° F.             20,000                                           Appearance      (unstable)   ok (stable)                                      ______________________________________                                    

Non-crosslinked sodium polyacrylates (ALCOGUM® 9710, AN10 and 296W) wereused in place of the crosslinked anionic suspending agents and again itwas found that about ten times the quantities of the non-crosslinkedmaterial was needed to achieve stability for two weeks at 120° F., asshown in Examples 37-39. The substantial increase in polymer percentagesignificantly reduced the lather and changed the lather feel-the latherbeing much more slippery than the compositions including an anioniccrosslinked polymeric suspending agent. Further, two of thenon-crosslinked sodium polyacrylates (Examples 37 and 38) were notstable for 2 weeks at 120° F.

    ______________________________________                                        EXAMPLES 37-39                                                                FORMULATION            37      38      39                                     ITEM   COMPONENT       WT. %   WT. %   WT. %                                  ______________________________________                                        1      sodium lauryl   27.5    27.5    27.5                                          sulfate (30% active)                                                          ALCOGUM ® 9710                                                                            25.0    --      --                                            (12% active)                                                           3      ALCOGUM ® AN10                                                                            --      30.0    --                                            (10% active)                                                           4      ALCOGUM ® 296W                                                                            --      --      20.0                                          (15% active)                                                           5      cocamide MEA    2.0     2.0     2.0                                    6      cetyl/stearyl   2.0     2.0     2.0                                           alcohol                                                                7      non-volatile    3.0     3.0     3.0                                           silicone blend                                                                75% SF 96-50                                                                  25% SE-30 GUM                                                          8      AROSURF ® TA-100                                                                          1.5     1.5     1.5                                    9      ammonium lauryl 27.5    27.5    27.5                                          sulfate (30% active)                                                   10     soft water      6.9     1.9     11.9                                   11     isopropyl myristate                                                                           2.0     2.0     2.0                                    12     ammonium xylene 2.0     2.0     2.0                                           sulfonate                                                              13     color, fragrance,                                                                             q.s     q.s     q.s                                           preservative                                                           ______________________________________                                    

OBSERVATIONS:

The "oil-phases" were all extremely thick. Upon dilution, the batchesremained fairly viscous. An additional 2% ammonium xylene sulfonate hadto be added to adequately thin the batches down.

    ______________________________________                                        RESULTS:                                                                                37       38         39                                              ______________________________________                                        pH at 80° F.                                                                       8.5        6.8        6.9                                         viscosity   10,000 cps 17,000 cps 5000 cps                                    TA          80,000 cps 120,000 cps                                                                              36,000 cps                                  ______________________________________                                    

What is claimed is:
 1. A hair conditioning shampoo compositioncomprising an emulsion of water; about 5 to about 65 percent by weightof an anionic cleaning surfactant; from about 0.1 to about 20 percent byweight of a cationic di-long chain alkyl quaternary nitrogen-containingconditioning agent, wherein the long alkyl chains bonded to the nitrogenatom have from about 12 to about 22 carbon atoms per alkyl chain; fromabout 0.5 to about 10 weight percent of a long chain fatty alcoholhaving about 8 to about 32 carbons in the long chain; from about 0.5 toabout 10 weight percent of a non-volatile silicone; and about 0.1 toabout 5% of an anionic cross-linked polymeric suspending agent selectedfrom the group consisting of an acrylamide/sulfonic acid copolymer and aterpolymer of maleic anhydride, a vinyl ether, and a straight orbranched chain diene having double bonds at the first and last positionsand a carbon chain length of C₅ -C₁₈.
 2. The hair conditioning shampoocomposition according to claim 1 wherein said non-volatile silicone ispresent in an amount of about 1.5 to about 5 percent by weight of saidcomposition.
 3. The hair conditioning shampoo composition according toclaim 1 wherein said quaternary nitrogen-containing conditioning agentis a quaternary ammonium salt containing two alkyl radicals having acarbon chain length from about 12 to about 18 carbon atoms per radical.4. The hair conditioning shampoo composition according to claim 1wherein said quaternary nitrogen-containing conditioning agent ispresent at about 1 percent to about 3 percent by weight of thecomposition.
 5. The hair conditioning shampoo composition according toclaim 1 wherein said long chain fatty alcohol is present in an amount ofabout 2 to about 5 weight percent of said composition.
 6. Thecomposition of claim 1 wherein the non-volatile silicone has a viscosityat 25° C of at least 5 centistokes and a boiling point at 760 mm Hgpressure and 25° C. of at least 250° C.
 7. The composition of claim 1wherein the polymeric suspending agent is a cross-linked terpolymer ofmaleic anhydride, methyl vinyl ether and a diene having a carbon chainlength of C₅ -C₁₈ with double bonds at the first and last positions. 8.The composition of claim 7 wherein the diene has a carbon chain lengthof 10 carbon atoms and is present in an amount of about 0.1% to about 3%by weight of the composition.
 9. The hair conditioning compositionaccording to claim 1 wherein said long chain fatty alcohol is selectedfrom the group consisting of cetyl alcohol, stearyl alcohol and mixturesthereof.
 10. The hair conditioning composition according to claim 1wherein said quaternary nitrogen-containing conditioning agent isselected from the group consisting of (a) compounds having two longcarbon chains and two identical or different short chain alkyl groupscontaining one to four carbon atoms bonded to the quaternary nitrogenatom, (b) compounds having two long carbon chains, one benzyl group andone short chain alkyl group having one to four carbon atoms bonded tothe quaternary nitrogen atom, and (c) compounds having two long carbonchains, one hydrogen atom and one short chain alkyl group having one tofour carbon atoms bonded to the quaternary nitrogen atom.
 11. In a hairconditioning shampoo composition containing water, a fatty alcohol, anon-volatile silicone and a quaternary nitrogen-containing conditioningagent, the improvement comprising the conditioning agent having only twolong chain alkyl groups bonded to the quaternary nitrogen atom, and ananionic polymeric suspending agent selected from the group consisting ofan acrylamide/sulfonic acid copolymer and a terpolymer of maleicanhydride, a vinyl ether, and a straight or branched chain diene havingdouble bonds at the first and last positions and a carbon chain lengthof C₅ -C₁₈, in an amount of about 0.1% to about 5% by weight of thecomposition.
 12. A method of shampooing and conditioning hair whichcomprises applying to said hair the composition of claim
 1. 13. A methodof shampooing and conditioning hair simultaneously which comprisesapplying to said hair the composition of claim
 12. 14. A method ofmanufacturing the conditioning shampoo composition of claim 1comprising:heating a mixture of water, the anionic, polymeric suspendingagent, and an anionic surfactant to a temperature above the meltingpoint of the fatty alcohol; adding the fatty alcohol to said heatedwater until said alcohol is completely melted to form an anionic alcoholsolution; adding the non-volatile silicone to said alcohol solution toform a two-phase composition; vigorously agitating the two-phasecomposition to break up the silicone into droplets; adding the di-longchain alkyl quaternary nitrogen-containing conditioning agent before orafter said vigorous agitation while maintaining the temperature of thetwo phase composition at or above the melting point of said conditioningagent to form a stable emulsion having a viscosity of about 5,000centipoises to about 20,000 centipoises.
 15. The method of claim 14further including adding 1-20% of the water and a proportionate quantityof the anionic surfactant to the composition after said vigorousagitation.
 16. The method of claim 14 wherein said non-volatile siliconeis present in an amount of about 1.5 to about 5 percent by weight ofsaid composition.
 17. The method of claim 14 wherein said quaternarynitrogen-containing conditioning agent is a quaternary ammonium saltcontaining two alkyl radicals having a carbon chain length from about 12to about 18 carbon atoms per radical.
 18. The method of claim 14 whereinsaid quaternary nitrogen-containing conditioning agent is present atabout 2 to about 3 percent by weight of the composition.
 19. The methodof claim 14 wherein said long chain fatty alcohol is present in anamount of about 2 to about 5 weight percent of said composition.
 20. Themethod of claim 14 wherein the non-volatile silicone has a viscosity at25° C. of at least 5 centistokes and a boiling point at 760 mm Hgpressure and 25° C. of at least 250° C.
 21. The method of claim 14wherein the polymeric suspending agent is a cross-linked copolymer ofacrylamide and a sulfonic acid.
 22. The method of claim 21 wherein thecross-linked resin is a polymer of ##STR3## wherein n=2-10,000, and ispresent in an amount of about 0.1% to about 3% by weight of thecomposition.
 23. The method of claim 14 wherein said long chain fattyalcohol is selected from the group consisting of cetyl alcohol, stearylalcohol and mixtures thereof.
 24. The method according to claim 23wherein said quaternary nitrogen-containing conditioning agent is aquaternary ammonium salt containing two alkyl radicals having a carbonchain length from about 12 to about 18 carbon atoms per radical.